In the 1980's, there was extensive research into lithium metal rechargeable batteries, particularly using sulphides, but also selenides, as cathode materials. Many lithium metal/molybdenum disulphide (Li/MoS2) batteries were produced but these were withdrawn following an incident in which a fire was attributed to the malfunction of such a battery. Other sulphides, such as iron disulphide FeS2, titanium disulphide TiS2 and selenides, such as niobium triselenide NbSe3 have also been particularly investigated as alternative cathode materials.
Although the use of lithium metal rechargeable batteries is now limited for reasons of safety, they are still used in the laboratory testing of materials. Lithium metal primary batteries using iron disulphide cathodes are manufactured.
Virtually all modern lithium rechargeable batteries are of the lithium-ion type, in which the negative electrode (anode) comprises lithium absorbed into a carbon support. These use a lithium containing cathode material, which is usually lithium cobalt oxide LiCoO2 although lithium nickel oxide LiNiO2, lithium manganese oxide LiMn2O4 and mixed oxides are also known to have been used.
Due to their high cost, the use of lithium rechargeable batteries at present is mainly limited to premium applications, such as portable computers or telephones. To gain access to wider markets, for example in applications such as the powering of electric vehicles, the cost must be reduced. Hence there is a strong demand for the high performance obtainable from lithium-ion batteries at much more economical prices.
On first inspection, the use of sulphides as cathode materials is not as attractive as the use of oxides. This is because the voltage achievable from sulphides is generally only about half of that achievable using corresponding oxides. However, the capacity of batteries incorporating sulphide based cathodes, measured in ampere hours per gram of material, is about 3 times greater than corresponding batteries incorporating oxide based cathodes. This leads to an overall advantage of about 1.5 times in terms of cathode energy density for batteries with sulphide based cathodes. A further advantage is that iron sulphides, in particular ferrous sulphide (FeS) and iron disulphide (FeS2) are inexpensive materials which may be dug out of the ground as natural occurring minerals. By contrast, lithium cobalt oxide is an expensive material, due mainly to the high cost of cobalt metal.
Binary transition metal sulphides are however not suitable for direct use in lithium-ion cells as they do not contain lithium. Lithium transition metal ternary sulphides, such as lithium molybdenum sulphide, lithium titanium sulphide, lithium niobium sulphide and lithium iron sulphide have been suggested as electrode materials for batteries (see for example, Japanese Kokai No 10208782 and Solid State lonics 117 (1999) 273–276). The conventional synthesis of lithium iron sulphide is via a solid state reaction in which lithium sulphide, Li2S, and ferrous sulphide, FeS, are intimately mixed together and heated under an inert atmosphere at a temperature of ca. 800° C. The reaction is diffusion controlled and the kinetics are slow. Consequently, the reaction can take up to 1 month at temperature to reach completion. This is highly inconvenient and is costly in terms of energy input. The economics of this synthesis for battery production are clearly unfavourable.
On a laboratory scale, lithium iron sulphide can be made by an electrochemical synthesis route in which a lithium metal/iron disulphide cell is discharged, and the lithium metal is removed and replaced by a carbon anode. This process however, is not amenable to scaling up. A further laboratory synthesis of lithium iron sulphide is the solid state reaction of lithium nitride, Li3N, with iron disulphide, FeS2, but again, this method is unsuitable for large scale use because of the high cost and shock sensitivity of lithium nitride.
The applicants have developed an economical synthesis which can be operated on a large scale to produce sulphides which have useful electrochemical properties.